Manufacture of vat dyes



in) Drawing. Application filed April 9,. 931,

Patented June 27,1933

fs'ra'resl Peru ARTHUR enoaen' PERKIN, on LEEDS, Annette 'sianrnnanson, on CHOBLTON- CUM-HARDY, menounsran, AND NORMAN neuron HADDOCK, or PREs'rwIcH;

MANCHESTER, ENGLAND, ASSIGNGBIS T IMPERIAL ITED, OF WESTMINSTER, ENG-LAND MAN FACTU E on This invention relates to the manufacture of vat dyes and it comprises processes where-' in a hydroxylated anthranol is reacted with an alkylating agent and a tetrahalogenothiophen, the alkylating agent and the terahalogenothiophen being either simultane ously or successively reacted iwith the anthranol, and it further comprises the vat dye stuffs thus obtained; all ascmore fully here'- inafter set forth and as claimed. I

We have found that when a hydroxylated anthraquinone, e. g. alizarin, is first reduced to the corresponding;anthran olhaving the probable formula H2 OH and then heated in an inert medium acting as a solvent or diluent, e. g. trichlorobenzene or naphthalene, with a tetrahalogenothiophen, for example, tetraohlorothiophen, and

an alkylatingagent, e. g. dimethyl sulphate v and with the addition, if desired of an acid dyes;

w We have further found that these new dyestuffs may be also obtained by reacting. a i tetrahalogenothiophen with a hydroXy-alkyloxyanthranol Either tetrachlorothiophen or tetrabromothiophen may be advantageously used as the tetrahalogenothiophen compound. As the hydroxyalkoxyanthranol compound, 4 hydroxy- 3 alkoxyanthranol having the probable formula:

whereinR represents an alkyl group, is advantageous' in our process.

Our invention thus-comprises the produc-' tion of new vat dyes by interaction, simul- Y taneously with or subsequent to alkylation,

1 of a hydroxylated anthranolwith tetra+ VAT nYns serial in) 528,972, and in Great Britain A ra/17, 1930.

halogenothiophen. When We apply our in- :HnarIcA mnns'rrzrns LIM- vention toffor example, the dihydroxyanthranol obtained from aliZarin we produce a beautiful green dye having among other valuable properties anexcellent fastness to chlorlne; we obtain a s milar dye when, wlth- :out simultaneous alkylation, we treat, for example, 4-hydro2ry-3-methoxyanthranol with tetrachlorothiophen. v halogenated'to produce further new vat dyes The processes given ante all produce valuable dyestuffs. These dyestuffs maybe represented by the probableformula': Y

wherein represents an alkyl group. From their structure it will, be seen that these dyestufl's may be consideredtas compounds obtainable .by reacting av hydroxylated ani I wherein Ri represents hydrogen or an alkyl group, a tetrahalogenothiophen, the alkyl group, if not present in the starting material,"

' beingintroduced by thealkylating agent durji gcthe reaction. a

l 1 Our invention is illustrated but not limited byithe following exampies, in which the'p'arts are by ,weight. a

i EWWZ 27. 5: parts of ,alizarine, 250 parts dust, 2500 parts of water and 350 parts of The product may be i of zinc ammonia (specific gravity 0.880) are mixed together and heated to boiling with vigorous stirring during hour. The reaction mixture is filtered and the filtrate run into a mixture of 2000 parts of per cent hydrochloric acid and 3000 parts of water. This procedure effects precipitation of the anthranol compound. The anthranol is filtered off, washed until free from acid, and dried in a vacuum at 100 C. The anthranol thus obtained may be represented by the probable forinulaz 20 parts of the dry powder so obtained are mixed with lOO parts of commercial trichlorobenzene, which contains tet'rachlorothiophen, 30 parts of dry sodium'carbonate, and 30 parts of dimethyl sulphate. The mixture is heated, with good stirring, to 190200 C. for 3 hours. The product is filtered off after cooling and washed with methylated spirit and water. It is a dark green powder, soluble with a bright red colour in sulphuric acid, and yielding a bluish-green vat, from which. cotton is dyed in bright emerald green shades. The dyestuffs may be represented by the following probable formula:

Example 2 5 parts of the anthranol prepared as in Example 1, 5 parts of tetrachlorothiophen, 50 parts of naphthalene, 7 .5 parts of dimethyl-sulphate, and 7 .5 parts of dry sodium carbonate, are mixed together and heated to boiling with good stirring for 6 hours. The mixture is cooled, and hot benzene is added. It is again cooled and'worked up asdItEX- ample 1. i

Ewample 3 5 parts of 1hydroXy-3-methoxyanthranol having the probable formula:

5 parts of tetrachlorothiophen and 50 parts of naphthalene are mixed and heated to boiling for 6 hours. The mixture is cooled, and hot benzene is added. It is again cooled and the product is filtered off and washed with Example :4.

10 parts of l-hydroxy-3-methoxyanthranol, 10 parts of tetrabromothiophen and 100 parts of naphthalene are mixed and boiled under reflux for 5 hours. After cooling to 100 C. 200 parts of boiling benzol are added. The hot mixture is filtered and the residue washed with hotbenzol until all naphthalene isremoved. The product so obtained is identical with that of Examples 1, 2 and 3.

As many apparently widely different embodiments of this invention may be made wlthout departing from the spirlt and scope thereof, it is to be understood that we do not intend to limit ourselves to the specific embodiments thereof except as indicatedin the appended claims.

We claim:

1. In the manufacture of vat dyestuffs, the process which comprises reacting a hydroxylated anthranol having the probable formula wherein R represents hydrogen or a methyl tetrahalogenothiophen group with a dimet-hyl sulphate and a tetrahalogenothiophen- 2. The process of claim 1 in which said is tetrachlorothiophen. 5 .v

3. The process of claim 1 in wliichthe reaction with the dimethyl sulphate and the tetrahalogenothiophen are simultaneously effected. u

4.'The process of claim1 inwhich the reaction with the dimethyl sulphate" and the tetrahalogenothiophen are successively effected.

of claim 1 in which the reaction is efi'e'cted in the presence of an inert solvent or diluent.

6. In themanufacture of vat dyes, the step which comprises reacting a hydroxylated anthranol .compound having the probable formula I 5. The process wherein R represents hydrogen or a methyl process which comprises simultaneously'reacting 3:4-dihydroxy'anthranol with 'dimethyl sulphate andwa tetrahalogenothiophen. r e I 8. The process of claim 7 in-which the said tetrahalogenothi'ophen is tetrachlorothiophen.

9. In the manufacture of vat dyes, the

process which comprises mixing together 3 4-dihydroxyanthranol, dimethyl sulphate and tetrachlorothiophen in an inert medium,

' heating the mixture thus obtained until rep I g '15. The process of claim 12 in which said action is effected,and isolating and recoverering the vat dyestuflsthus produced.

10. The process of claim 9 in which said inert medium is naphthalene.

11. In the manufacture of vat dyestuffs, the process which comprises reducing alizarin to the corresponding hydroxylated an- I thranol, mixing the anthranol compound thus obtained with trichlorbenzene, dimethyl sulphate, and tetrachloro'thiophen, heating the mixture to a temperature between 190 to 200 C. untilreaction is effectedandisolat-n ing thevat dyestuffs thus obtained.

process which comprises, reacting l-hydroxy- -methylanthranol with a tetrahalogenothiophen in the presence of an inert medium and p v v I which cotton is dyed in bright emeraldisolating the vat dyestuff thus obtained.

13. The process of claim 12 in which said inert medium is naphthalene. I

14. The process of claim 12 in which said tetrahalogenothiophen is tetrabromothiohen.

12. In the manufacture of vat dyes the tetrahalogenothiophen is tetrachlorothiohen.

16.'In the manufacture of vat dyestuffs,

the process which comprises mixing together 4-hydroxy-3-methoxyanthranol and tetra- T chlorothiophen with naphthalene, heating the,

mixture until reaction is effected, cooling the reaction mixture and adding hot benzene,

filtering ofl' vthe vat dyestuff thus obtained i and washing the vat dyestufi thus obtained with henzol. i

17. As new products, vat dyestufl's having v the probable formula wherein R represents an hydrogen or a methyl group, said dyestuffs, being dark 1 green powders soluble with a bright red "colorin sulphuricacid and yielding a bluishgreen vat from which cottonis dyed in bright emerald-green shades.

18. As a new product, a vat dyestufi' havingthe probable formula:

OCH:

II vO said dyestuff being a dark green powder soluble with a bright red color in sulphuric acid andyielding a bluish-green vat from green shades.

.In testlmony whereof we aflix our signa ARTHUR GEORGE PERKIN.

ARNOLD SHEPHERDSON; NORMAN HULITON HADDOCK. 

